Latex coating compositions



United States Patent 33192561 LATEX COATENG (IQMPGSETEGNS Wilbur M.Sullivan, Bloomfield, and Leonard A. Carlson, Murray Hill, NJ.,assignors to Union Carbide Corpora= tion, a corporation of New York NoDrawing. flriginal application Oct. 1, 1959, Ser. No. 843,635, newPatent No. 3,047,525, dated July 31, 1961. Divided and this applicationNov. 30, 1961, Ser. No. 156,163

13 Claims. (Cl. 26t29.6)

This invention relates to surface coating compositions and especially tonovel polyvinyl acetate latex compositions which, when applied to basematerials as a surface coating, will produce self-induced threedimensional effects. The invention further relates to articles ofmanufacture consisting of various base materials having on the surfacethereof a decorative as well as protective coating derived from ournovel coating compositions.

Latex coatings are now well known in the protective coatings field. Thewidespread utility of such coatings has been the result of intensiveresearch and the consequent development of emulsion polymerizationtechniques which permit the polymerization or copolymerization of avariety of monomers to produce high molecular weight polymers having, ingeneral, outstanding resistance properties and especial suitability forparticular coatings uses. The fact that latex coating systems utilizewater as the carrier or application medium results in tremendouseconomic savings and also enables the production of coatingscompositions that are nontoxic, nonfiammable and odorless. One of thefurther, more important advantages flowing from the use of latex systemsis the ability to apply coatings at or above 50 percent solids content,by weight, and subsequently obtain dry films of the thickness normallydesired in a protective coating with ordinary brush, spray, roller, dipor blade methods. The application consistency is independent of themolecular weight of the polymer in the latex and the consistency dependsrather upon the composition of the exterior or aqueous phase. Adjustmentof the consistency of the aqueous phase is generally achieved throughthe addition of minor amounts of water soluble or colloidallydispersible materials that are well known to those skilled in the art. Afurther advantage obtainable through the use of latex coating systems isthe ability to apply uniform coatings to porous, normally absorbentsubstrata such as kraft paper. Latexes in general will not penetrate norbe absorbed in such substrata. This hold out characteristic is ofspecial value in applying sealer coatings to plaster, wallboard, paperand textiles. The formulation techniques for latex based coatings usefulon a wide variety of surfaces such as exterior masonry, interior plasterand gypsum board, paper, cloth, metal and other base materials has nowadvanced to the point where the effects of certain additives, e.g.,pigments, fillers, plasticizers, filming agents, surface active agentsand other modifiers are generally understood. As a result certainprinciples of compounding latexes are now generally accepted and latexsystems successfully compete with established coating compositions inmost of the fields in which coatings are now used.

A very significant exception to this general utility or adaptability ofemulsion polymer compositions for surface coatings has existed, andcontinues to exist, in the field of self-textured coatings. As used inthis application, the term self-textured coatings is to be construed asmeaning coatings or surface finishes which develop patterns or texturedappearances during the drying cycle which patterns or texturedappearances give the effect of being three dimensional when viewed bythe human eye. These effects, as implied by the term self are the directresult of forces developed within the coating composition itself ratherthan the result of any external manual or mechanical operations upon thecoating either during or after the application of the coatingcomposition to the base material. Although certain such effects havepreviously been achieved using solvent based coatings, there are to ourknowledge no water based coating compositions employing non-homogeneousor polyphase dispersions, such as synthetic latex polymer compositions,which will form such self-induced three dimensional efiects when appliedto the surface of the base material which is to be protected andsimultaneously decorated.

A further significant exception to the general utility of latexcompositions as surface coatings has existed in the field of finishescontaining metallic pigments. For example, in coatings pigmented withmetallic aluminum powder or flakes, non-latex systems have beennecessitated since the aluminum would react with any water present andhydrogen would be evolved. Similar problems exist when other powdered orflaked metallic pigments, e.g., powdered copper, bronze, brass, zinc,etc. are used. This problem, insofar as aluminum pigments are concerned,has recently been solved by methods described in US. Patent 2,858,230 toKnoll et al. This patent relates in general to special methods ofpreparing a metallic aluminum-containing pigment which may be used inwater based paints, i.e., latex coating compositions. Similar methods,modified as described hereinafter, enable the manufacture ofself-texturing coatings compositions containing metallic pngments suchas bronze, brass, copper, etc., in lieu of aluminum; when such isdesired.

The desirability of having self-induced pattern forming coatingcompositions based on the use of an aqueous vehicle or film former (thatis, self-texturing latex coating compositions) becomes immediatelyapparent when one considers the inherent advantages of such compositionssuch as those previously mentioned, i.e., low application consistencywhich is not dependent upon the molecular weight of the polymer withinthe latex and excellent hold out on porous substrata such as paper andpaper board, as well as other advantages such as the greatly increasedfreedom from the fire hazards and toxicity problems generally involvedwhen resin solution coating compositions are utilized. In addition thereis the further advantage that no curing or oxidation of the applied filmis required when water based coating compositions are used since dryingin this case is a simple matter of allowing the volatiles to escape fromthe film. Such can be accomplished by a nominally brief heating atelevated temperatures after the coating has been applied and the patternhas formed. For example, heating for about two minutes at about 250 F.Will normally be sufficient to dry the coating. This speed of drying isadmirably suited to the processing schedules of present commercial papercoating equipment and is moreover highly desirable in cases Where therequirement for quick drying is not so demanding. Pattern finishesderived from latex coating compositions also ofier other distinctadvantages over the conventional solvent type pattern forming coatingcompositions such as, for example, the resistance to oxidation, ultraviolet light degradation, and to the action of greases, oils and alkalisobtainable when a polyvinyl acetate latex is utilized.

It is therefore a primary object of this invention to provide novelself-texturing water based coating compositions and methods by which thesame may be prepared. It is a further obiect of this invention toprovide methods for applying our novel latex coating compositions to thebase surface of a base material so as to form a self-inducedthree-dimensional, patterned finish on said surface; which finish maythen be finally a dried. It is a further object to provide an article ofmanufacture having a patterned surface coating derived from the novelcoating composition of this invention.

In general, the coating composition of this invention is comprised ofthe following ingredients or components in the indicated proportions,each of which will be further defined hereinafter:

A. Polyvinyl acetate latex.We have found that the objects of thisinvention may be accomplished only through the use of a polyvinylacetate latex having certain specific properties as indicatedhereinafter.

B. Pattern forming agent.The pattern forming agent is a liquid organicmaterial preferably having a relatively fast evaporation rate andpreferably strongly hydrophobic in character.

'0. Aqueous dispersion of non-leafing metallic powder (when desired).Dispersions of powdered aluminum prepared as taught by Knoll et al.,U.-S. Patent 2,858,230 and treated with an ammonium phosphate in orderto obtain storage stability are desirably used in the practice of thisinvention. Similar dispersions wherein powdered bronze, brass, copper,etc., are directly substituted for the aluminum may also be used. Theuse of a metallic powder as pigment in my novel compositions of matteris preferred because of the very pleasing decorative effects which maybe thereby obtained.

Other materials well known in the surface coating art may also be added,e.g., fillers, pigments and other colorants, thickening agents, etc.These further optional additives must not be strongly acidic or stronglybasic.

The principle and underlying criteria on the use of these furtheroptional additives are that the latex emulsion must not be broken andthe aluminum powder must not be attacked, nor its protective phosphatecoating removed.

The essential characteristics and properties of the ingredients in ournovel self-texturing latex coating composition are as follows:

A. POLYVINYL ACETATE LATEX The polyvinyl acetate latex required for thepractice of this invention contains a homopolymer prepared by emulsionpolymeric action, said polymer having an average particle size range of0.75 to 3.0 microns. The emulsifying agents and stabilizers employed forpolymerization are chosen with certain limitations in mind. Thepreferred emulsifier is a nonionic type, while the preferred stabilizeror protective colloid is hydroxyethyl cellulose. Methods of preparingthe polymer containing latexes are well known in the art. For thepurposes of our invention the combination of emulsifier and protectivecolloid is balanced so as to result in a latex of a vinyl acetatepolymer having a particle size range of about 0.75 to 3.0 microns; saidlatex having a nonvolatile content of 45-65 percent (preferably 57-60percent) by weight, a surface tension of at least 48 dynes/cm.(preferably at least 52 dynes/cm.) and a pH of about 4 to about 8(preferably 4 to 6). Residual monomer content within the acceptablecommercial limits, i.e., less than about 1%, is satisfactory. Thepresence of strongly anionic emulsifiers and protective colloids willtend to prevent pattern formation. When these components are stronglyalkaline, and a powdered metallic pigment is used, a stable, non-gassingsystem may not be obtainable. The property which appears to be mostdominant is the surface tension. Latexes having a surface tension of notless than 48 dynes/cm. and preferably not less than 52 dynes/cm. areessential for the satisfactory practice of this invention. Example 1(below) clearly illustrates the importance of this factor. Latexescontaining polyvinyl acetate copolymerized with up to 20% of anothervinyl monomer may also be used if the necessary requirements noted aboveare fulfilled.

B. A PATTERN FORMING AGENT The pattern forming agent of our invention isa liquid organic material which evaporates at a rapid rate and thusproduces the driving force or energy for selfinduced pattern formation.The organic liquids used for this purpose are preferably stronglyhydrophobic, i.e., practically insoluble in water.

In our copending application S.N. 843,634, filed on even date herewith,we have disclosed and claimed pattern forming agents useful in preparingself-texturing coatings compositions which, when applied to varioussubstrata, form hammered eflt'ect coatings upon said substrata. In orderto obtain this effect, pattern control agents are necessary, as well aspattern forming agents.

For the purposes of the instant invention, herein disclosed and claimed,pattern control agents are not necessary. The compositions produced byfollowing the teachings of this invention will yield decorativeself-induced, patterned finishes when applied to the surfaces of varioussubstrata, but will not yield hammertone finishes. The most importantpattern forming agents used in the practice of this invention are theunsubstituted medium boiling range (about 110 C. to about 200 C.) liquidaliphatic hydrocarbons and those mixtures of unsubstituted aliphatichydrocarbons commonly known as mineral spirits which have boiling pointswithin this same range. Also useful are the ethyl silicates which, asshown in Example 4 below, aid in the production of a highly desirablefine dot pattern of obvious wide utility. It is to be especially notedthat lower boiling aliphatic hydrocarbons (Examples 7 to 9) are notuseful for producing self-textured coatings from latex compositions.Similarly, hydrophilic materials are not useful (-see Examples 5 and 6)The amount of pattern forming agent used in the practice of ourinvention is in the range of from about 20 parts to parts by weight forevery 100 parts by weight of polyvinyl acetate solids in the latex base.

C. AQUEOUS DISPERSION OF NON-LEAFIN METALLIC POWDER Although the use ofa metallic pigment is not neces sary for the practice of this invention,it is preferred that such pigments be incorporated in our coatingcomposition because of the very pleasing decorative effects therebyobtainable.

We have found that only certain specific types of metallic pigments maybe used if the self-texturing coating composition of our invention areto be obtained. A particularly useful metallic pigment is powderedaluminum, and the methods by which it may be satisfactorily used will bedescribed as exemplary.

The aforementioned Knoll et a1. patent describes generally the properuse of aluminum pigments in latex coating compositions. However, theteachings of this patent and the modifications suggested therein resultonly in latex coating compositions which when applied to vthe surface ofa base material or substrate give smooth finishes. Satisfactoryself-textured finishes are not obtained when the patentees suggestionsare completely and fully followed.

A non-leafing grade of aluminum powder is a necessary ingredient of thedispersion used for this invention. For example, aluminum powders havinga negligible leafing Parts Water 65 Diammonium hydrogen phosphate 1.1 to1.7 Non-ionic surfactant 0.45 to 0.90 Aluminum powder 35 The preparationof these aqueous dispersions is basically as follows: Dissolve thediammonium hydrogen phosphate and the surfactant in water making surethat the surfactant is completely dispersed by allowing to stand forapproximately minutes, then add the aluminum powder. A normal mixingtime required for completely dispersing the aluminum powder within thesolution should be approximately another 10 minutes. Be sure that noneof the dry pigment remains un-wetted by the phosphate solution. Thealuminum paste thus prepared should be permitted to age for 24-48 hoursin a loosely covered container before mixing with the water based binder(e.g. polyvinyl acetate latex) This period is necessary to insuresufiicient time for the phosphate to react completely with the aluminumto form a barrier coat which renders the aluminum passive.

In practicing this invention, we have found that mono basic and dibasicammonium phosphates are of equal utility. An ammonium phosphate must beused as the stabilizing agent in our invention. Other phosphates, e.g.tetrasodium pyrophosphate, known to be especially effective as a pigmentdispersing agent, do not produce a passive aluminum dispersion, evenwhen used in conjunction with an ammonium phosphate.

Any suitable non-ionic surfactant may be used. For the purposes of thisinvention the only criterion for determining suitability of thesurfactant is that it should not markedly reduce the surface tension ofthe coating composition and thus tend to prevent patern formation.Tergitol T MN (trimethyl nonyl ether of polyethylene glycol) has beenfound quite satisfactory for the purposes of this invention in aidingthe Wetting out of the aluminum powder without preventing or adverselyaffecting pattern formation in the applied coating. Other suitablesurfactants will be apparent to those skilled in the art, or may beeasily determined by routine check tests to determine the eifect of saidsurfactants on the surface tension of the coating composition.

The dispersing techniques heretofore described may be varied to someextent without departing from the basic necessity of passivating thealuminum. The ratio of water to aluminum may be varied over aconsiderable range and the amount of phosphate stabilizing agent may beincreased to about twice the amount above specified without any illeffects. The 24-28 hour aging period may be reduced to about 12 hours orless (as little as one hour if found necessary), but aging periods ofless than about 10 hours are usually found to result in increaseddifiiculties insofar as stability of the powdered metal dispersion isconcerned. Aging periods may also be increased to several weeks withoutaffecting the desired result of selfinduced textured patterns in theapplied coating. For best overall results it is preferred to age'themetallic pigment dispersion for at least 24 hours before furtherprocessing.

It should be reemphasized that pigment dispersions containing powderedmetals other than aluminum may also be prepared and used in the practiceof this invention. In all cases, the powdered metal used must be ofnon-leating quality, and an ammonium phosphate stabilizer must be used.Example 11 below shows the preparation of a selftexturing coatingcomposition containing, as a direct substitute for aluminum, anon-leafing grade of bronze powder. Other metallic powders, e.g.,copper, brass, etc. may be similarly used.

It should also be reemphasized that although the use of a metallicpigment is preferred, self-induced pattern effects may also be obtainedusing the basic composition described above with the powdered metal andammonium phosphate entirely omitted. Alternatively, we may substitutefor the powdered metal other pigments such as flake mica (approximately160 mesh) or rutile titanium dioxide without materially affecting thetype of selftextured coating finally obtained.

D. OTHER ADDITIVES The use of hydrophobic compounds may be resorted tofor the production of discontinuous films which yield attractivedecorative efiects when applied over a background of contrasting color.Such'compounds include oleic acid, cetyl alcohol'and mineral orlubricating oils. Also useful for this purpose are aromatic hydrocarbonsand chlorinated aliphatic hydrocarbons. Certain proprietary compounds,such as Triton X45 and Ucon Lubricant LB285 may be used in conjunctionwith the above materials to aid in the development of specific efiects.Triton X-45 is a non-ionic surface active agent having a chemicalformula and structure of:

and made by reacting t-octyl phenol with ethylene oxide. Ucon LB285 is amonobutyl ether of polypropylene glycol having a F. viscosity ofapproximately 285 SUS (Saybolt Universal seconds). Additives to combatacidity and confer poor wetting characteristics can also be used.

A plasticizer for the resin may be used to increase the flexibility ofthe coating where necessary for the use intended. Ordinarily up to 15percent, based on the weight of the latex solids, of any suitablecompound recognized as an effective plasticizing agent for polyvinylacetate, e.g., dibutyl phthalate, tricresyl phosphate, etc., may beadded. The plasticizer may be added by stirring into the latex beforecompounding the coating composition of this invention but preferably isadded by stirring into the coating composition after the latex has beenadded. Pre-emulsification of the plasticizer may be used where necessaryto achieve a finely divided dispersion of plasticizer types which resiststir-in addition.

Control of application consistency is achieved by adding a watersolution of hydroxyethyl cellulose. Other thickeners suitable for latexsystems such as natural gums (e.g. guar gum), modified starches andmethyl cellulose may be used. Colloidal clays, bentonite clay andalkaline polyacrylates will tend to give gassing problems and thereforeshould not be used in our latex coating composition. It is believed thatthese latter compounds are unsatisfactory because they selectivelyiabsorb or otherwise remove and disperse the passivating and stabilizingphosphate layer on the aluminum particles.

E. COLORING EFFECTS In order to obtain certain decorative effects it mayfrequently be desirable to incorporate pigments or other colorants inour latex coating composition. We have, for example, prepared a suitablechromium oxide coloring composition by wetting 65 parts by weight ofchromium oxide pigment with a solution of 1.3 parts of a nonionicsurfactant (e.g., alkyl phenyl ether of polyethylene glycol known asTergitol NPX) in 35 parts by water. When this colorant dispersion isadded to our polyvinyl acetate latex coating composition in variousamounts ranging generally from about 0.2 to 10% or more by weight of drycolor, based on the total composition, there are produced self-texturedhammer finishes having a very attractive green tint, with the colordepth corresponding roughly to the quantity of colorant added.Similarly, other commercially produced aqueous pulp and paste colors canbe used if routine check tests give assurance that the dispersants usedto prepare these color dispersions are not detrimental to the stabilityof the aqueous dispersion of metallic powder (when used) and are notsufficiently active to efiectively reduce the surface tension of thepolyvinyl acetate latex and thus prevent the development of theselfinduced pattern effects in the final coating, as previouslyexplained. Principal types of color pigments have been found to besatisfactory including oxides, phthalo cyam'ne blues and greens, carbonblack, Hansa yellow and toluidine red. When using a compositioncontaining a metallic pigment the amount of colorant ordinarily used isfrom about 0.2 to 1.0% by weight of dry color based on the weight of thetotal composition. In a composition for producing nonmetallic finishesup to 10% or more by weight of dry color may be used to obtain anycertain desired shade of color in the coating as applied.

The preferred method for applying the self-texturing latex coatingcomposition of our invention is by spraying from an ordinary paint spraygun operating in the normal 30 to 60 p.s.i. range. Blade coating methodsand dip coating techniques have been used satisfactorily to produceself-induced hammer effects from the latex coating composition of theinvention herein described. Interesting textures and patterns can beobtained by using roller coating devices. It is interesting to notehowever that in this case the roller type paint applier used in ordinaryhousehold painting does not create a finish having a self-induced hammereffect while machine roller type coaters are quite satisfactory. Thisdifference in results is most probably explained by the fact thatmachine rollers have smooth surfaces and are not constructed of thefibrous materials such as the lambs wool, nylon fluff, etc. .used inmaking household-type paint rollers. In normal operation, therefore,machine rollers lay down a smooth film of uniform thickness even whenused in applying materials of poor leveling ability; whereas the manualhousehold-type roller lays down a very rough textured Wet film and canonly be used with paints having very good leveling qualities.

The following specific examples are given to further illustrate thepractice of this invention. It is understood that these examples aremerely illustrative of the practice of our invention and are not to beconstrued as limiting the scope of this invention other than as definedin the appended claims.

Example 1 In this example a series of coating compositions were preparedto show the effect of surface tension of the polyvinyl acetate latexupon the ability of the latex coating composition to form self-texturedcoatings. In this test the following standard formula was used.

Ingredient Pounds Gallons Non-leafing aluminum powder 37. 41 1. SPolyvinvyl Acetate Latex (58% non-volatiles) 297. 72 32.01 Water 318. 8438. 23 Tri cresyl Phosphate Plasticizer 8. 63 0.88 Apcothinner 1 136. 6518. 87 Hydroxyethyl Cellulose (7.5% non-volatile solution). 19. 55 2. 30Trimethyl Nonyl ether of Polyethylene Glycol (Tergitol TMN) 0. 91 0.11Monobasic Ammonium Phosphate 1.12 0.07

To l 820. 83 94. 27

NorE.-The total composition is based on 100% by weight.

1 Medium boiling Range (117-142" C.) aliphatic hydrocarbons:Parafiins53%; also contains napthenes35% and (Le. cycloaliphatics);aromatics-12%.

In order to prepare the latex coating compositions the manufacturingprocedure was as follows:

First: The aqueous dispersion of non-lea-fing aluminum powder wasprepared by adding the various components to a paint mixer sequentiallyin the following order: 40% of the water from the above standardformula, ammonium phosphate, non-ionic surfactant (e.g. trimethyl nonylether of polyethylene glycol), and the non-leafing aluminum powder.Agitation was continuous during each addition and each component wasthoroughly dispersed before the next was added. The aluminum paste wasthen allowed to age for a period of 24 hours before it was incorporatedin the latex coating composition.

Second: The latex coating composition (i.e., the paint) was prepared bymixing the following ingredients in the order named: aluminum paste(prepared by the above procedure), polyvinyl acetate latex, tricresylphosphate plasticizer, remainder (i.e., 60%) of the Water in the abovestandard formula hydroxyethyl cellulose solution, and finallyApcothinner (pattern forming agent) A number of commercially availablepolyvinyl acetate latexes and polyvinyl copolymer latexes wereincorporated in the above noted standard formula, following theprocedure as set forth immediately above in each instance. Results wereas follows:

The data of Table I is self-explanatory, clearly illustrating theextreme importance of using a polyvinyl acetate latex having a surfacetension of at least about 48 dynes/ cm. and preferably at least 5 2dynes/cm.

Example 2 The latex coating composition of Example 1 containingcommercial resin 'B in the standard formulation was sprayed on cardstock using an ordinary paint spray gun operating at 30-80 psi. Thecoating was then dried for two minutes in a 250 F. oven. An attractive,continuously repeating, irregular island patterned finish was produced.

Examples 3 and 4 These examples give illustrations of other patternforming agents useful in our invention. In these examples the standardformulation and manufacturing procedures of Example 2 were used toprepare several self-texturing polyvinyl acetate latex coatingscompositions with the exception that the pattern forming agents shown inTable H below were directly substituted for the Apcothinner used inExample 2. Results were as follows, with the data for Apcothinnerrepeated for comparison.

TABLE II Concentration (Parts/ Boiling Example Agent Parts poly- PatternPoint of vinyl acetate Agent, solids in latex) C.

2 Apcothinner 100 Irregular 117-142 Islands Varsol 100 do 161-197 4 40%Ethyl Silicate 100 Fine Dot 168 Aqueous Solution. Structure.

1 Medium boiling range aliphatic hydrocarbons.

In similar fashion, novel latex coatings compositions utilizing unmixedliquid aliphatic hydrocarbons boiling between about 110-200 C. in lieuof the Apcothinner of Example 2, may be prepared, which compositionswill form self-induced patterned finishes when applied to the surface ofvarious substrata.

Examples -9 These examples are included solely to give illustrations ofmaterials unsatisfactory for use as pattern forming agents in thepractice of my invention. In these examples the materials listed belowwere directly substituted for the Apcothinner used in Example 2. None ofcompositions containing the listed materials yielded a regular patternwhen applied to card stock as described in Example 2.

a mixture of Apcothinner and toluene in a weight ratio of 1:3. The latexcoating composition containing this agent when applied to card stock asdescribed in Example 2 gave a novel discontinuous self-textured coating,but the continuously repeating pattern of Example 2 was no longerpresent.

Example 11 Direct substitution of non-leafing bronze powder for thenon-leafing aluminum power in Example 2 gave a coating composition whichwhen supplied to the surface of a base material gave a very decorativegold-colored selfinduced pattern similar to that obtained in Example 2.

Example 12 This example is the same as Example 2 with the exception that5% by weight (based on the total latex coating composition) of a 25%water dispersion of copper phthalocyanine green was added, an attractiveand decorative green tinted patterned effect similar to that of Example2 was produced.

The self-texturing coating compositions of this invention are useful indecorating all types of surfaces made from a wide variety of materialsincluding metal, wood, paper, fiber stocks, cloth and plaster. producedaccording to the teachings of this invention are useful for numerousmanufactured articles such as, for example, cabinets, office furniture,manufacturing equipment and housings therefor, wrapping papers,wallpaper, ceiling tile, wall boards and other wall covering material.

Polyvinyl acetate latex coating compositions which produce self-texturedcoatings according to the teachings of this invention are believed torepresent a very desirable advance in the art of pattern finishformulation in that water is the primary vehicle for the coatingmaterials. Excell nt control and reproducibility of pattern type andsize has been achieved. Storage of exemplary formulations for periods ofsix months or more has resulted in no significant change in the abilityof these compositions to develop the same self-induced patterns observedwhen the compositions were used immediately after original preparation.The addition of aqueous dispersions of pigment and other colorants maybe achieved by simple stirin mixing techniques and permits theproduction of selftextured coatings having a wide range of colors andtints without the necessity of resorting to milling or grindingoperations.

The present application is a division of copending application SerialNo. 843,635, filed October 1, 1959, now Patent 3,047,523, issued July31, 1961.

Coated materials I We claim: I

1. A polyvinyl acetate latex composition for producin self-inducedtextured coatings consisting essentially of:

(a) a polyvinyl acetate latex having: a non-volatile content of fromabout 45 to about 65 percent by weight, a surface tension of atleastabout 48 dynes/ cm, a pH within the range of from about 4 to about 8,and wherein the said polyvinyl acetate has a particle size of from about0:75 to about 3.0 microns; and

(b) for every 100 parts by weight of polyvinyl acetate solids in saidlatex from about 20 to about 100 parts by weight of a liquid aliphatichydrocarbon having a boiling point in the range of from about 110 C. toabout 200 C.

2. A polyvinyl acetate latex composition for producing self-inducedtextured coatings consisting essentially of:

(a) a polyvinyl acetate latex having: a non-volatile content of fromabout 57 to about 60 percent by Weight, a surface tension of at leastabout 52 dynes/ cm., a pH within the range of from about 4 to about 6,and wherein the said polyvinyl acetate latex has a particle size of fromabout 0.75 to about 3.0 microns; and

(b) for every 100 parts by weight of polyvinyl acetate solids in saidlatex from about 20 to about 100 parts by weight of a liquid aliphatichydrocarbon having a boiling point in the range of from about 110 C. toabout 200 C.

3. A polyvinyl acetate latex composition for producing self-inducedtextured coatings consisting essentially of:

(a) a polyvinyl acetate latex having: a non-volatile content of fromabout 45 to about 65 percent by weight, a surface tension of at leastabout 48 dynes/ cm., a pH Within the range of from about 4 to about 8,and wherein the said polyvinyl acetate has a particle size of from about0.75 to'about 3.0 microns;

(b for every 100 parts by weight of polyvinyl acetate solids in saidlatex from about 20 to about 100 parts by weight of a liquid aliphatichydrocarbon having a boiling point in the range of from about 110 C. toabout 200 C.; and,

(c) for every 100 parts by weight of polyvinyl acetate solids insaid-latex, from about to about 50 parts by weight, based on the solidscontent thereof, of a stable aqueous dispersion of a non-leafingmetallic powder, said dispersion containing ammonium phosphate as thesole stabilizing agent.

4. A polyvinyl acetate latex composition for producing self-inducedtextured coatings consisting essentially of:

(a) a polyvinyl acetate latex having: a non-volatile content of fromabout 45 to about '65 percent by weight, a surface tension of at leastabout 48 dynes/ cm., a pH within the range or" from about 4 to about 8,and wherein the said polyvinyl acetate has a particle size of from about0.75 to about 3.0 microns; and

(b) for every 100 parts by weight of polyvinyl acetate solids in saidlatex from about 20 to about 100 parts by Weight of mineral spiritshaving a boiling point range of from about 110 C. to about 200 C.

5. A composition as defined in claim 4 wherein the said mineral spiritscontain about 53 percent by weight paraffins and have a boiling pointrange of from about 117 C. to about 142 C. and wherein the amount ofsaid mineral spirits is about 100 parts by weight for every 100 parts byweight of said polyvinyl acetate solids.

6. A polyvinyl acetate latex composition for producing self-inducedtextured coatings consisting essentially of: (a) a polyvinyl acetatelatex having: a non-volatile content of from about 45 to about 65percent by weight, a surface tension of at least about 48 dynes/ cm., apH within the range of from about 4 to about 8, and wherein the saidpolyvinyl acetate has a particle size of from about 0.75 to about 3.0microns;

(b) for every 100 parts by weight of polyvinyl acetate solids in saidlatex about 100 parts by weight of mineral spirits boiling in the rangeof from about 117 C. to about 142 C. and containing about 53 percentparaflins.

(c) for every 100 parts by weight of polyvinyl acetate solids in saidlatex from about 15 to about 50 parts by weight, based on the solidscontent thereof, of a stable aqueous dispersion of a non-leafingmetallic powder, said dispersion containing ammonium phosphate as thesole stabilizing agent.

7. A polyvinyl acetate latex composition for producing self-inducedtextured coatings consisting essentially of:

(a) a polyvinyl acetate latex having: a non-volatile lCOI1t11t of fromabout 45 to about 65 percent by weight, a surface tension of at leastabout 48 dynes/ cm., a pH within the range of from about 4 to about 8,and wherein the said polyvinyl acetate has a particle size of from about:75 to about 3.0 microns;

(b) for every 100 parts by weight of polyvinyl acetate solids in saidlatex about 100 parts by weight of mineral spirits boiling in the rangeof from about [117 C. to about 142 C. and containing about 53 percentparaffins; and

(c) for every 100 parts by weight of polyvinyl acetate solids in saidlatex from about 15 to about 50 parts by weight, based on the solidscontent thereof, of a stable aqueous dispersion of non-leafing aluminumpowder, said dispersion containing ammonium phosphate as the solestabilizing agent.

8. A polyvinyl acetate latex composition for producing self-inducedtextured coatings consisting essentially of:

(a) a polyvinyl acetate latex having: a non-volatile content of fromabout 45 to about 65 percent by weight, a surface tension of at leastabout 48 dynes/ cm., a pH within the range of from about 4 to about 8,and wherein the said polyvinyl acetate has a particle size of from about0.75 to about 3.0 microns;

(b) for every 100 parts by weight of polyvinyl acetate solids in saidlatex about 100 parts by weight of mineral spirits boiling in the rangeof from about 117 C. to about 142 C. and containing about 53 percentpraflins; and

-(c) for every 100 parts by weight of polyvinyl acetate solids in saidlatex from about 15 to about 50 parts by weight, based on the solidscontent thereof, of a stable aqueous dispersion of non-leafing bronzepowder, said dispersion containing ammonium phosphate as the solestabilizing agent.

9. A polyvinyl acetate latex composition for producing self-inducedtextured coatings consisting essentially of:

(a) a polyvinyl acetate latex having: a non-volatile content of fromabout 57 to about 60 percent by 12 weight, a surface tension of at leastabout 52 dynes/ cr'n., a pH within the range of from about 4 to about 6,and wherein the said polyvinyl acetate has a particle size of from about0.75 to about 3.0 microns; *(b) for every 100 parts by weight ofpolyvinyl acetate solids in said latex about 100 parts by weight ofmineral spirits boiling in the range of from about 117 C. to about 142C. and containing about 53 percent paraflins; and (c) for every 100parts by weight of polyvinyl acetate solids in said latex about 22 partsby weight, based on the solids content thereof, of a stable aqueousdispersion of non-leafing aluminum powder, said dispersion containingammonium phosphate as the sole stabilizing agent. 10. A polyvinylacetate latex composition for producing self-induced textured coatingsconsisting essentially of: (a) a polyvinyl acetate latex having: anon-volatile content of from about 57 to about 60 percent by weight, asurface tension of at least about 52 dynes/ cm., a pH within the rangeof from about 4 to about 6, and wherein the said polyvinyl acetate has aparticle size of from about 0.75 to about 3.0 microns; (b) for everyparts by weight of polyvinyl acetate solids in said latex about 100parts by weight of mineral spirits boiling in the range of from about117 C. to about 142 C. and containing about 53 percent paraflins; and(c) for every 100 parts by weight of polyvinyl acetate solids in saidlatex about 22 parts by weight, based on the solids content thereof, ofa stable aqueous dispersion of non-leafing bronze powder, saiddispersion containing ammonium phosphate as the sole stabilizing agent.11. An article of manufacture comprising a base material having on thesurface thereof a self-induced textured coating, said coating being theresidue produced by applying the composition of claim 1 to said surfaceand drying.

12. An article of manufacture comprising a base material having on thesurface thereof a self-induced patterned coating, said coating being theresidue produced by applying the composition of claim 3 onto saidsurface and drying.

13. An article of manufacture comprising a base material having on thesurface thereof a self-induced textured coating, said coating being theresidue produced by applying the composition of claim 4 onto saidsurface and drymg.

References Cited in the file of this patent UNITED STATES PATENTS2,508,092 Beynon May 16, '1950 2,858,230 Knoll et al. Oct. 28, 1958

1. A POLYVINYL ACETATE LATEX COMPOSITION FOR PRODUCING SELF-INDUCEDTEXTURED COATINGS CONSISTING ESSENTIALLY OF: (A) A POLYVINYL ACETATELATEX HAVING: A NON-VOLATILE CONTENT OF FROM ABOUT 45 TO ABOUT 65PERCENT BY WEIGHT, A SURFACE TENSION OF AT LEAST ABOUT 48 DYNES/ CM., APH WITHIN THE RANGE OF FROM ABOUT 4 TO ABOUT 8, AND WHEREIN THE SAIDPOLYVINYL ACETATE HAS A PARTICLE SIZE OF FROM ABOUT 0.75 TO ABOUT 3.0MICRONS; AND (B) FOR EVERY 100 PARTS BY WEIGHT OF POLYVINYL ACETATESOLIDS IN SAID LATEX FROM ABOUT 20 TO ABOUT 100 PARTS BY WEIGHT OF ALIQUID ALIPHATIC HYDROCARBON HAVING A BOILING POINT IN THE RANGE OF FROMABOUT 110*C. TO ABOUT 200*C.